Switchable adhesives

ABSTRACT

The present invention provides switchable adhesives comprising a mixture, in proportions by weight, of 20% to 98% of an adhesive, 2% to 80% of curable molecules and 0.05% to 10% of photoinitiator in which the weight proportion of the adhesive is calculated on the basis of its dry weight and wherein the adhesive includes an internal cross-linker for cross-linking the adhesive during drying to provide a cohesive strength of between 5 and 100 N/12.7×12.7 mm measured according to FINAT test method No. 18. Preferably, the adhesive and curable molecules are mutually soluble when dry, or the curable molecules and adhesive may be uniformly dispersed in each other. Preferably the amount of adhesive in the mixture is in the range 40% to 98% by weight, more preferably 60% to 95% by weight, even more preferably 70% to 85% by weight. Preferably the proportion of curable molecules in the mixture ranges from 2% to 60% by weight, more preferably 5% to 40% by weight, even more preferably 15% to 30% by weight. Preferably, the photoinitiator is present in the mixture in the proportions 0.5% to 5% by weight, more preferably 1% to 3% by weight. Such switchable adhesives are useful in medical dressings and other removable sheet products, and may be simply prepared by stirring the adhesive, the curable molecules and the photoinitiator together at room temperature.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. patent application Ser. No.13/638,304 filed on Sep. 28, 2012, which is a national stage entry ofPCT Application No. PCT/GB11/00495 filed on Mar. 31, 2011, which claimsthe benefit of European Application No. EP 10003556.7 filed Mar. 31,2010.

The present invention relates to adhesives, more particularly topressure sensitive adhesives that are “switchable” from a tacky state toa non-tacky or low-tack state in which the switched adhesive has areduced peel strength relative to the peel strength of the adhesivebefore switching. The present invention also relates to methods forproducing switchable adhesives and to articles comprising switchableadhesives.

In particular, the present invention provides benefits in situationswhere strong adhesion to fragile surfaces is required. Should it thenbecome necessary to release the fragile surface, the adhesive can beswitched to its low-tack state and removed from the fragile surfacewithout harming it.

Certain adhesive products, such as adhesive surgical or medicaldressings and bandages normally comprise a layer of a pressure sensitiveadhesive. However, when a conventional adhesive dressing and/or bandageis removed from the patient's skin, it can often cause localised traumaand/or pain to the patient. This is particularly true for patients witha long term condition that requires an adhesive dressing to be appliedto the same part of the body repeatedly over a prolonged period, such asstoma patients. It is also true for patients with fragile skin,especially the elderly and children.

Therefore, a need has been identified to provide adhesive dressings, forexample, which are able to undergo a reduction in peel strength of theadhesive, and therefore cause less localised trauma to the patient'sskin upon removal of the dressing, compared to a dressing using aconventional adhesive. Further, a need has been identified to providesuch adhesive dressings where the reduction in peel strength can beachieved in a controlled manner in a relatively short time, say from anumber of seconds to a few minutes.

For convenience, the term “switchable” will be used to refer toadhesives which can be changed from a tacky to a non-tacky state or,more accurately, to a low-tack state. Recognizing that the expression“low-tack” is a relative term, it will be defined here as meaning thecondition of minimum tackiness which the adhesive reaches afterswitching from its tacky state. The reduction in peel force may be asgreat as 99% or as little as 30%. Typically, the reduction in peel forceis between 70 and 90%.

Examples of known switchable adhesives may be found in U.S. Pat. No.5,032,637, U.S. Pat. No. 5,352,516, U.S. Pat. No. 4,331,576 and U.S.Pat. No. 5,182,323 which describe adhesives that become less tacky,i.e., are switchable, upon contact with water. However, such adhesivesare unsuitable if used on a wound dressing and the patient's wound needsto be kept dry.

UV switchable adhesives are described in U.S. Pat. No. 4,286,047, U.S.Pat. No. 4,968,559, U.S. Pat. No. 5,118,567, U.S. Pat. No. 5,187,007 andJapanese Patent No. 3043988. The adhesives disclosed in these documentssuffer from the disadvantage that they require high doses of UVradiation and need to be used in conjunction with photoinitiators thatwould be regarded as hazardous if used in medical applications requiringskin contact. Since it is undesirable to expose patients to too muchultra violet radiation, these earlier patents do not satisfy the needfor a switchable adhesive which can undergo a reduction in peel strengthat low dosages of UV radiation or, more preferably, by exposure tovisible light irradiation.

European Patent No. EP 0863775 and U.S. Pat. No. 6,184,264 and U.S. Pat.No. 6,610,762 disclose adhesives that are switchable when exposed to,inter alia, visible light, i.e., are visible light switchable or areswitchable upon exposure to low dosages of UV light. The visible lightswitchable or low dosage UV light switchable adhesives described inthese documents generally comprise an acrylic adhesive based oncopolymers of alkyl acrylates, acrylic acid and/or a free radicalpolymerisable vinyl moiety “modified” or functionalised by a curablemoiety bound thereto. That is to say, the adhesive backbone ischemically combined with curable moiety to form a single chemicalcompound. Typical of the bound-in curable moieties are those derivedfrom anthracenes, cinnamates, maleimides, coumarins, acrylates and/ormethacrylates.

United States published patent application No. US 2004/0019127 A1discloses a UV-curable pressure-sensitive adhesive compositioncomprising a photoinitiator with a molar absorptivity at 365 nm of atleast 1,000 mol-1·cm-1 and a maximum absorption wavelength of at least420 nm on a long wavelength side; and an adhesive sheet having a layerof the composition disposed over a photo-transmitting base film. Thepressure-sensitive adhesive sheet can be cured by exposure toultraviolet rays even at a low intensity or for short time, whichcontributes to energy saving and productivity improvements as a sheetfor processing, fixation or surface protection of a semiconductor wafer.

U.S. Pat. No. 4,999,242 discloses an adhesive tape having an adhesivecurable by irradiation, for example by ultra violet rays or ionisingradiation such as an electron beam, comprising a radiation-curableadhesive layer formed on a radiation transmitting-substrate. Theradiation-curable adhesive layer is composed of an acrylic adhesive, acompound having carbon-carbon double bonds and a silicone acrylatecompound. The radiation-curable tape can be used in processing steps forthe production of semiconductor wafers, ceramics and glass employing adirect picking-up system.

U.S. Pat. No. 5,942,578 discloses an energy beam curable pressuresensitive adhesive composition which comprises at least two energy beamcurable copolymers having energy beam polymerizable groups in sidechains thereof. The adhesive composition has satisfactory adhesivestrength before irradiation with the energy beam and can be cured byirradiation to a degree such that the amount of adhesive residueremaining on an adherend after peeling is extremely small. Thecomposition ensures excellent expansibility at the expanding step andexcellent recognition at the time of pickup. Also, the compositionexhibits high work efficiency because of very low pickup strength at thebonding step, irrespective of the execution of the expanding step.

U.S. Pat. No. 5,955,512 discloses a pressure sensitive adhesivecomposition comprising an acrylic copolymer (A), an energy beampolymerizable urethane acrylate oligomer (B) and an energy beampolymerizable compound having one acryloyl group or methacryloyl groupin each molecule thereof (C). The composition preferably also contains aplasticizer (D), a cross-linking agent (E) and/or a photo-polymerizationinitiator (F) according to necessity. The pressure sensitive adhesivecomposition has satisfactory pressure sensitive adherence and initialadhesion before irradiation with an energy beam and the adhesivestrength thereof is sharply reduced whilst maintaining its elasticityafter irradiation. The pressure sensitive adhesive composition is saidto ensure excellent chip alignability in the expanding step subsequentto dicing.

U.S. Pat. No. 5,747,551 discloses a UV curable pressure sensitiveadhesive composition which comprises in proportions by weight: about0.1% to about 15% of a photoinitiator agent, about 10% to about 80% of apolyurethane resin with a pendent acrylate functionality, zero to about70% by of an acrylate monomer, about 0.1% to about 25% by weight of a anacrylated polybutadiene component, and zero to about 50% by weight of atackifier agent. Such a composition allows efficient cross-linking ofhigh T_(g) oligomers or polymers by coupling the polymerisationmechanism to an extremely low T_(g) vinyl-terminated rubber. However,the composition disclosed in this reference is not switchable becausethe functionality of the curable species in the composition is such thatthey do not give rise to sufficient cross-linking to effect switchingfrom a tacky state to a non-tacky state.

One problem associated with the use of adhesives that are functionalisedby bound-in curable groups is the difficulty in synthesis. Thepolymerisation of some prior art functionalised adhesives requires theuse of multiple solvents in order to:

-   -   (a) produce a polymer having a sufficiently high molecular        weight and low monomer concentration for it to be used as a        medical adhesive, and    -   (b) carry out the reaction between the functionalising moiety        and the main polymer chain.

An adhesive manufacturing process requiring multiple solvents, and hencesolvent exchange steps, becomes complicated, time-consuming andexpensive. There may also be environmental concerns about disposal ofwaste solvents.

Another problem associated with adhesives functionalised by curablegroups that are not bound-in is the reduction in cohesive strength thatoccurs when the curable molecules are blended into the adhesive polymer.If the basic polymer backbone has an acceptable cohesive strength forthe intended application, the addition of unbound curable moleculesreduces the cohesive strength, with the result that the product to whichthe switchable adhesive composition is applied can move due to coldcreep and hence is not fixed in position. This is particularlyinappropriate for wound dressings, especially when applied to a part ofthe patient's body that flexes, because the creep may result in theadhesive becoming exposed on the skin without a backing layer, resultingin stained residuals left on the skin for days.

The Tack-Shear Balance

The adhesives used in pressure sensitive adhesives (PSAs) areviscoelastic materials, meaning that they have both viscous and elasticproperties. A high tack (high peel) PSA will be dominated by its viscousproperties and will flow out, wet and fill cavities well on the surfaceto which it is applied. This means not only that it will give high peelforce values but also that it flows when shear forces are applied for along period of time. On the other hand a PSA in which the elasticproperties dominate will sustain shear forces well over time but,because it does not flow and wet the surface to which it has beenapplied very well, the resulting resistance to peel will be low. Thismeans that, during formulation, of a PSA it is of importance to balancethe tack and corresponding shear properties so that they fulfill theintended product specification. Since a PSA's tack-shear balance isdependent on polymer chain length, intra molecularly forces, intramolecularly entanglement, etc., different PSAs will end up havingdifferent tack-shear behavior. For example, a water borne acrylicadhesive has, in general, a poorer tack-shear balance than a solventborne acrylic adhesive. Since different PSA-containing products, havedifferent demands due to their intended applications, e.g., applicationor residence time, size, imposed shear and peel force, etc., it is ofgreat importance to be able to control the tack-shear balance.

The present invention has been made in view of the above disadvantagesof known switchable pressure sensitive adhesive systems and takingaccount of the tack-shear balance discussed above. The inventionprovides the following advantages:

-   -   (1) Adjustment of performances such as switch %, switch time,        peel strength, cohesive strength, etc., is easier and more        quickly done by changing the ingredients in a mixture or by        changing the concentration of them, rather than synthesising a        new adhesive polymer.    -   (2) The production time for a switchable PSA based on a mixture        is a few hours, while that for synthesising a switchable        adhesive polymer compound as described in the prior art is a        matter of days.    -   (3) By using a higher number of curable groups in a switchable        PSA based on a mixture compared to that which can be achieved in        a switchable adhesive compound having bound-in curable groups,        the decrease of tackiness can be made greater while the switch        time can be brought down to seconds rather than minutes.    -   (4) The concentration of the most expensive component, the        photoinitiator, can be decreased considerably compared to the        amount of photoinitiator required in a prior art switchable        adhesive due to the higher concentration of curable groups    -   (5) The switchable PSA according to the invention can be made        using commercially available ingredients at a comparable low        price and supplied in an ample variation; the end cost of the        switchable PSA is much less compared to switchable adhesive        polymer compounds synthesised with bound-in curable groups.    -   (6) The production hazard is much less for a switchable PSA        based on a mixture rather than based on a switchable adhesive        polymer compound synthesised with bound-in curable groups        because the mixing can be done under ambient temperature without        any chemical reaction taking place. This minimizes the risk of        gelling in production vessels or runaway exothermic reactions.

An embodiment of the present invention provides an improved switchableadhesive formulation that can be manufactured without the use ofmultiple solvents. An embodiment of the present invention provides animproved switchable adhesive system which undergoes transformation froma tacky state to a non-tacky state in a relatively short period of timecompared to known switchable adhesive systems. An embodiment of thepresent invention provides an improved switchable adhesive system whichundergoes transformation from a tacky state to a non-tacky state uponexposure to visible light and without requiring exposure to UVradiation.

In a first aspect, the invention is a switchable pressure sensitiveadhesive (PSA) composition comprising a mixture, in proportions byweight, of 2% to 80% of curable molecules that are curable by freeradical polymerisation, 0.05% to 10% of photoinitiator and an internalcross-linker that is cross-linkable by mechanism other than free radicalpolymerisation for cross linking the adhesive, the balance being baseadhesive polymer and incidental constituents and the weight proportionsbeing calculated on the basis of the dry weight of the base adhesivepolymer, the PSA having a cohesive strength of between 5 and 100N/12.7×12.7 mm measured according to FINAT test method No. 18. Thecohesive strength may be significantly higher than 30N/12.7×12.7 mmdepending on the application for which the switchable PSA is intended.Preferably, the base adhesive polymer and curable molecules are mutuallysoluble when dry, although good results are still obtained when thecurable molecules are uniformly dispersed in the adhesive even when theadhesive and curable molecules are mutually insoluble or only partlymutually soluble when dry.

The cohesive strength of the composition is determined by controllingthe cohesive strength of the adhesive polymer backbone, and this is doneby partially cross-linking it.

Cross-linking can be achieved by incorporating monomers of e.g.N-methylol acrylamide, N-(iso-butoxymethylene)acrylamide, methylacrylamidoglycolate methyl ether (all 0.5-5%) or metal chelates, e.g.,acetylacetonates of Zr, Al, or Fe (up to 2% of polymer weight) into thepolymer backbone which then cross-links during drying after spreading ona substrate.

Al and Ti acetylacetonates and similar compounds can also be added afterthe polymerization step in concentrations between 0.1 and 2% of thepolymer weight and used as an internal cross-linker through utilizingcarboxylic groups in the polymer backbone during the drying step.

Multi functional isocyanates like toluene diisocyanate (TDI), trimethylhexamethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI), orisophorane diisocyanate (IPDI), can be used to chemically inter linkhydroxylic or carboxylic functions of different polymer chains, added inconcentrations up to about 1% of the polymer weight.

Internal cross-linking can also be achieved between the carboxylicgroups in the polymer backbone and added amino resins such as melamine,benzoguanamine, glycoluril, urea derivatives e.g. hexamethoxymethylmelamine, methoxymethyl methylol melamine, methoxymethyl ethoxymethylbenzoguanamine, tetrabutoxymethyl glycoluril, butoxymethyl methylol urea(up to 6%).

The above mentioned cross-linking can also be achieved usingpolycarbodiimides or multifunctional propylene imines.

It is also possible to blend one or more polymers having high cohesivestrength with one or more polymers having low cohesive strength in orderto achieve the desired balance.

Cross-linking is also important for effective switching and it istherefore necessary to distinguish between the type of cross-linkingthat is undertaken for controlling the cohesive strength of the adhesivecomposition and the type of cross-linking that brings about switching.In the first case, cross-linking for controlling the cohesive strengthof the adhesive is effected using an internal cross-linker, i.e., across-linker supplied with or forming part of the adhesive polymerbackbone material. In the second case, cross-linking for switching iseffected by visible light or UV-induced curing of the curable moleculesto form a three-dimensional polymeric network entangling the chains ofthe base adhesive polymer backbone, thereby reducing their mobility andfree volume. Preferably the amount of base adhesive polymer present inthe mixture is in the range 20% to 98% by weight, more preferably 40% to90% by weight, and most preferably 50% to 70% by weight. Preferably theproportion of curable molecules in the mixture ranges from 2% to 80% byweight, more preferably 10% to 60% by weight, and most preferably 30% to50% by weight. Preferably, the photoinitiator is present in the mixturein the proportions 0.1% to 5% by weight, more preferably 0.5% to 2% byweight. Preferably, the photoinitiator is also soluble in the drymixture of adhesive and curable molecules, although it will be capableof exerting its curing initiating effect upon exposure to an activatinglight source if finely dispersed through the dry mixture but notdissolved in it.

The weight proportion for the base adhesive polymer is given here interms of its dry weight and excludes any solvent which might normally bepresent in a commercially available bulk adhesive.

In certain embodiments, the weight proportion of base adhesive polymeris from one of the following lower endpoints (inclusive), or from one ofthe following upper endpoints (inclusive). The lower endpoints are 20%,30%, 40%, 50%, 60% and 70%; the upper endpoints are 98%, 95%, 90% and85%. In certain embodiments, the weight proportion of curable moleculesis from one of the following lower endpoints (inclusive), or from one ofthe following upper endpoints (inclusive). The lower endpoints are 2%,5%, 10% and 15%; the upper endpoints are 80%, 70%, 60%, 50%, 40% and30%. In certain embodiments, the weight proportion of photoinitiator isfrom one of the following lower endpoints (inclusive), or from one ofthe following upper endpoints (inclusive). The lower endpoints are0.05%, 0.1%, 0.2%, 0.5% and 1.0%; the upper endpoints are 10%, 5%, 4%and 3%.

The incidental constituents may be one or more of stabilizers,tackifiers, light scattering particles, fungicides, colorants,humectants, etc.

The adhesive component may be a hydrocolloid having polymeric chainsextending from a core or nucleus, and the reference to the adhesive andthe curable molecules being mutually soluble in each other when dry isto be understood as meaning that the curable molecules and the polymericchains are mutually soluble in each other. Hydrocolloid-based medicaldressings may be used for skin and wound treatment. When first attachedto the skin, dry hydrocolloids are only slightly adherent to the skin,but quickly absorb moisture from the skin and become more tacky.

The preparation method for the switchable adhesive compositions of theinvention is very simple. The adhesive component, the curable molecules(monomers and/or oligomers) and the photoinitiator are mixed, preferablystirred, together in darkness or under red light conditions for about 30to 60 minutes, most conveniently at room temperature. The mixture alsoincludes the internal cross-linker. The internal cross-linker may beincluded as part of the base adhesive, for example obtained from acommercial supplier who supplies as a stock item base adhesive withinternal cross-linkers. Alternatively, the internal cross-linker may besupplied as a separate component from the base adhesive. The internalcross-linker may be added to the mixture as a solution. The adhesivecomponent is usually supplied in solution (typically, 40% to 60% solidsby weight); the solvent for the adhesive may be a suitable vehicle fordissolving the internal cross-linker. The curable molecules are usuallysolvent free, although some curable molecules of high viscosity may becarried in a solvent which also could act to stabilize the internalcross-linker; the photoinitiator is usually solid and the most difficultcomponent of the system to dissolve and/or disperse.

Following completion of the mixing together, the resulting compositionis spread onto, e.g., a release liner at a certain thickness—typicallyabout 60 μm when wet—and then left to dry at room temperature for about10 minutes. The release liner may be a polyethylene coated paper with asilicone compound chemically bound to the surface. The spread adhesiveis then further dried at 80-150° C. for 3 to 10 minutes. A slightlyhigher temperature and a longer drying time can be used if necessary.After drying, the thickness of the spread adhesive will typically beabout 30 μm.

The dried adhesive is then transferred onto a carrier film, for example,for peel strength and switching evaluation.

Alternatively, the dried adhesive may be transferred to a material for awound dressing, for example a web of polyethylene or polyurethane filmwhich may optionally be perforated, or a woven or non-woven fabric.

For a medical dressing or similar application, the adhesive componentmay be selected from polymers capable of forming shaped bodies, thinwalls or coatings. Suitable polymers are biologically andpharmaceutically compatible, hypoallergenic and insoluble in andcompatible with body fluids or tissues with which the dressing iscontacted.

Exemplary light transmitting materials for carrying the adhesive polymerlayer include polyethylene, polypropylene, polyurethane,ethylene/propylene copolymers, ethylene/ethylacrylate copolymers,ethylene/vinyl acetate copolymers, silicone elastomers, especially themedical-grade polydimethylsiloxanes, neoprene rubber, polyisobutylene,polyacrylates, chlorinated poly-ethylene, polyvinyl chloride, vinylchloride-vinyl acetate copolymer, cross-linked polymethacrylate polymers(hydrogel), polyvinylidene chloride, poly (ethylene terephthalate),butyl rubber, epichlorohydrin rubbers, ethylenevinyl alcohol copolymers,ethylene-vinyloxyethanol copolymers; silicone copolymers, for example,polysiloxane-polycarbonate copolymers, polysiloxanepolyethylene oxidecopolymers, polysiloxane-polymethacrylate copolymers,polysiloxane-alkylene copolymers (e.g., polysiloxane-ethylenecopolymers), polysiloxane-alkylenesilane copolymers (e.g.,polysiloxane-ethylenesilane copolymers), and the like; cellulosepolymers, for example methyl or ethyl cellulose, hydroxy propyl methylcellulose, and cellulose esters; polycarbonates;polytetrafluoro-ethylene; and the like.

The adhesives may be water-soluble, but will most often be soluble in,and hence commercially supplied as solutions in, organic solvents suchas ethyl acetate, hexane, toluene, acetone etc. Preferred adhesives arepolyacrylates, polyurethanes and polysilicones. Especially preferred arepolyacrylates. By the term polyacrylates is meant acrylate, methacrylateand acrylate copolymer adhesives. Indeed acrylate copolymer adhesivesare most preferred, e.g. alkyl acrylate copolymers. The most commonlyused monomers in polyacrylates are butyl acrylate, ethylhexyl acrylate,hydroxyethyl acrylate and acrylic acid. They may be used singly or in amixture, their relative proportions in the mixture being selecteddepending on the water penetration rate, viscoelastic properties, T_(g),etc., that it is desired to achieve.

Cross-linking can be achieved by incorporating monomers of e.g.N-methylol acrylamide, N-(iso-butoxymethylene)acrylamide, methylacrylamidoglycolate methyl ether (all 0.5-5%) or metal chelates, e.g.,acetylacetonates of Zr, Al, or Fe (up to 2% of polymer weight) into thepolymer backbone which then cross-links during drying after spreading ona substrate.

Al and Ti acetylacetonates and similar compounds can also be added afterthe polymerization step in concentrations between 0.1 and 3% of thepolymer weight and used as an internal cross-linker through utilizingcarboxylic groups in the polymer backbone during the drying step.

Multi functional isocyanates like TMDI, hexamethylene diisocyante, canbe used to chemically inter link hydroxylic or carboxylic functions ofdifferent polymer chains, added in concentrations up to 5%, for example1%, of the polymer weight,

Internal cross-linking can also be achieved between the carboxylicgroups in the polymer backbone and added amino resins such as melamine,benzoguanamine, glycoluril, urea derivatives e.g. hexamethoxymethylmelamine, methoxymethyl methylol melamine, methoxymethyl ethoxymethylbenzoguanamine, tetrabutoxymethyl glycoluril, butoxymethyl methylol urea(up to 6%).

The above mentioned cross-linking can also be achieved usingpolycarbodiimides or multifunctional propylene imines.

The backbone adhesive polymer used as the adhesive component of thecomposition must include a functional group that is able to reactchemically or physico-chemically with the internal cross-linker. It isalso possible to use, as the starting or base adhesive, one which ismanufactured with bound-in curable molecules; this is mixed with furthercurable molecules (not bound-in). The mechanism of internalcross-linking must not be a free radical mechanism because that is themechanism used for effecting cross-linking for the switching.

Preferably, the curable molecules and the adhesive are soluble in eachother when in the dry state, i.e., in the absence of a solvent.Alternatively, in the case that the adhesive and the curable moleculesare not mutually soluble in each other when dry, or are only partlymutually soluble, they are uniformly dispersed in the composition.Typically, the adhesive (or the base adhesive if a mixture of adhesivesis used) will be selected from polyacrylates, polyurethanes and siliconeadhesives.

In the broadest sense, any conventional known unsaturated compoundscould be used as the curable molecules, but preferred examples, usedalone or in mixtures, are curable molecules such as acrylic acid estersor methacrylic acid esters of alcohols, glycols, pentaerythritol,trimethylpropane, glycerol, aliphatic epoxides, aromatic epoxidesincluding bisphenol A epoxides, aliphatic urethanes, silicones,polyesters and polyethers, as well as ethoxylated or propoxylatedspecies thereof.

The curable molecules have more than one unsaturated site, i.e., greaterthan single functionality. Multiple functionalities of 3 or greater, ormore preferably 4 or greater are especially effective because curablemolecules of this type are able to form highly cross-linkedthree-dimensional polymeric networks which are an important feature ofswitching, as will be explained below. Also, many curable moleculeshaving multiple functionalities are commonly available at reasonablecost.

The radical initiator may be any species which is capable of producingradical species under the desired conditions but preferred examples arephotoinitiators able to start the radical reaction under mildconditions, e.g. visible light, in order to promote radicalpolymerization reactions in the curable molecules. As a consequence,when the photoinitiator becomes activated by exposure to visible light,the curable molecules form chemical bonds with other curable moleculesand hence create polymeric cross-linking. The effect of suchcross-linking is to build a three-dimensional polymeric networkentangling the adhesive polymer chains, thereby reducing their mobilityand free volume. The photoinitiator may alternatively produce radicalspecies under the mild conditions of long wave UV.

Curable molecules having multiple functionality are able to form highlycross-linked three-dimensional polymeric networks easily and henceexhibit good switching properties. The adhesive strength of the adhesivebecomes reduced and it becomes less tacky so that it may be peeled moreeasily from the surface to which it is attached.

The adhesive mixture preferably also contains stabilizers which areadded in order to prevent spontaneous cross-linking of the curablemolecules during storage. Examples of such stabilizers are hydroquinonessuch as 4-methoxy phenol (sometimes referred to as hydroquinonemonomethyl ether) and 2,4-ditert-butyl-metoxyphenol, or1-piperidinyloxy-4,4′-[1,10-dioxo-1,10-decanediyl) bis (oxy)]bis[2,2,6,6-tetra methyl] and pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

The adhesive mixture may also include photo-sensitisers. Since asensitising species often absorbs energy in a different part of thespectrum from the initiator, more effective use of the light source maybe achievable through the incorporation of sensitisers into the mixture.Many photo-sensitisers are complex organic molecules, absorbing in thevisible portion of the spectrum.

The adhesive mixture may also incorporate light scattering particles toincrease the effect of irradiation of the adhesive mixture. Preferably,the light scattering particles are an inorganic compound such as silicapowder, alumina powder, silica-alumina powder or mica powder withparticle sizes of the order of 10 nm or greater, typically up to 1 μm.

Any conventionally known free radical initiators may be used.Particularly preferred are those initiators which react to visible lightradiation, although initiators which react under shorter wavelengthlight may be used in compositions of the invention, depending on theapplication. Thus, free radical initiators which may be mentionedinclude titanocene photoinitiators; dye/co-initiator systems, e.g.,thionine/triethanol-amine; dye/borate salt systems; dye/peroxide systemsand 1,2-diketone/co-initiator systems, e.g., camphor-quinone/tertiaryamine.

Examples of visible light photoinitiators (which include Irgacure 784because it absorbs light both in the UV and visible spectrum) are:Benzildimethyl ketal; Phenanthrenequinone; Titanocenes (of whichIrgacure 784 is one example);Bis(2,4,6-trimethyl-benzoyl)-phenylphosphineoxide.

Examples of UV photoinitiators are: Benzoin and ethyl, isopropyl orisobutyl ethers of Benzoin; Benzophenone and hydroxy or methylbenzophenones;2-Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one; Acetophenoneand 4′-Phenoxyacetophenone; Benzoyl-biphenyl; Benzil; Anisoin, as wellas the Irgacures such as Irgacure 651 (benzyl dimethyl ketal) orIrgacure 907(2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one); or theUvatones, such as Uvatone 8302 (2,2-diethoxy-1,2-diphenyl ethanone).

Some photoinitiators contain phosphine compounds which will not receiveapproval by the medical regulatory authorities for use near the skin.However, phosphine-containing photoinitiators may be used in other,non-medical, applications.

Preferred free radical photoinitiators for medical applications are thetitanocene initiators such as bis.(.eta.5-cyclopentadienyl)-bis(2,6-difluoro-3-[pyrrol-1-yl]-phenyl) titanium, sold in the UK by CibaGeigy as Irgacure 784 (Trade Mark).

The present invention is not limited to use in adhesive dressings.Examples of other technical applications include:

Application Format Description Labels, posters A two or Labelscomprising an adhesive or Notices three-layer according to the presentinvention can design as be used in product tags, pricing tags, depictedin advertisement posters put onto the FIG. 3 or varnish of vehicles.There will result a FIG. 1. strong fixation and an easy removal withoutany adhesive residues left on the surface Or, in the case of a two layerfilm, easily removable residues after switching the remaining adhesive.Protection A two or Goods may get scratches during Films three-layertransportation, storage, handling etc; design as and by using anadhesive according to depicted in the present invention in combinationFIG. 3 or with protective films, the goods will FIG. 1. be protectedfrom scratches and similar surface damage; when removing the film, nostrong peeling force is necessary and, in the case of a three layerfilm, no adhesive residues left on the goods; or, in the case of a twolayer film, easily removable residues after switching the remainingadhesive. Fixation of A three-layer Products and/or product parts thatare Sensitive design as very fragile and/or have a sensitive PartsDuring depicted surface can be adhered to a substrate Manufacture or inFIG. 1. using an adhesive according to the Transport present inventionduring transportation or manufacturing processes for achieving a veryaccurate position and fixation; after processing, the product can stillbe detached from the adhesive when desired without high peel forces andwithout leaving residues on its surface. Shop Floor or A two-layer Usingan adhesive according to the Wall Marker design as present invention onshop floor marker Labels depicted labels in different shapes, a very inFIG. 3. strong fixation to the floor or wall surface is possible. Whenthe marker label is removed, adhesive residues may be left on thesurface which are very easy to rub off when switched. Wallpaper Athree-layer Using an adhesive according to the design as presentinvention on wall paper, a very depicted strong fixation to the wall ispossible. in FIG. 1. When the wallpaper is removed after switching theadhesive, the wall surface is left without any damage or residuals.Masking or A two or Using an adhesive according to the Fixationthree-layer present invention for the purpose of Tapes design astemporary fixation or masking, a very (fixation of depicted in strongfixation to the surface is non-fragile FIG. 3 or possible. When the tapeis removed or non- FIG. 1. after switching the adhesive using a delicatethree layer design, the surface is left articles) without any residuesor, in the case of a two layer film, easily removable residues afterswitching the remaining adhesive. De-bond on A two or Using an adhesiveaccording to the demand(DOD) three-layer present invention for thepurpose of applications, design as strongly attaching different such asopening depicted in components into a product or package. of packagesand FIG. 3 or When the product or package needs to recycling of FIG. 1.be disassembled, the light occlusive different layer is removed andafter switching materials in a the adhesive the different parts canproduct by easily be detached. Should adhesive detaching them residuesbe left on the component or after the end product surface, these can beeasily of service removed after switching the adhesive. life time.

Whilst it is preferable that the curable molecules in the mixture reactvia a free radical reaction, it is most desirable that the reaction ofthe curable molecules is visible light initiated through the use ofsuitable photoinitiators. Thus the wavelength of the light used may beless than 700 nm, e.g., preferably between 400 and 700 nm, particularlyless than 550 nm.

The dosage of light used may vary depending upon the switchable adhesivecomposition. When a visible light switchable adhesive is used, ambientlight may be used and therefore the dosage may vary according to theprevailing lighting conditions. When UV light is used, the dosage isgenerally greater than 0.4 mW·cm-1.

In a second aspect, the present invention provides a device or articleincorporating the switchable adhesive formulation of the first aspect ofthe invention. In particular, the device may be a medical device such asa first aid product, an ostomy device, intravenous (IV) tape, othersurgical tapes and adhesive bandages, patches which deliver therapeuticagents transdermally, skin closure products, wound dressings, etc.

For medical applications, the curable molecules used in the switchableadhesive preferably have a molecular mass greater than 500 dalton (Da),more preferably greater than 1000 Da, most preferably greater than 1500Da. Molecules of this size are generally understood to be incapable ofbeing absorbed through the skin and hence are less hazardous.

The adhesive mixtures of the invention are preferably pressure sensitiveadhesives (PSAs) and are particularly advantageous in the manufacture ofadhesive medical devices as mentioned above. The adhesives may also beuseful in the manufacture of other conventional products which require apeelable adhesive, e.g., masking tapes, stencils, etc.

According to a further feature of the invention an adhesive dressing isprovided comprising a backing layer substantially coated on at least onesurface thereof with an adhesive as hereinbefore described. The adhesivecoating may be a continuous coating or a non-continuous coating, e.g.,the adhesive may be spread in a pattern. A non-continuous coating ishelpful, for example, in improving air circulation and may assist inrendering wound dressings and surgical tapes “breathable”.

The backing layer preferably comprises a light occlusive layer and atransparent or translucent layer. By the term light occlusive layer ismeant, in particular, a layer which is occlusive over the wavelengthrange in which the photoinitiator absorbs. Especially preferred is alight occlusive layer that is occlusive to wavelengths below 700 nm. Thelight occlusive and transparent layers, if comprised of similarmaterials, may be laminated together by lightly pressing them togetherat the nip of a pair of heated rollers. Alternatively, they may bebonded together using a low peel strength adhesive on the surfacesfacing each other. Preferably, the light occlusive layer has the lowpeel strength adhesive on its surface facing the transparent layer andthe low peel strength adhesive remains attached to the light occlusivelayer when the layers are peeled apart. The light occlusive layer may bea peelable adhesive containing, e.g., titanium dioxide or carbon black.This enables a wide choice of colours to be adopted in the top layer.

The breathability properties of the backing layer must be such that itdoesn't block water transmission, otherwise the skin will get very moistunderneath the dressing. This may be detrimental to the health of theunderlying tissues and/or may result in loss of adhesion of the dressingprematurely.

Thus, in accordance with the second aspect of the invention mentionedabove, an adhesive dressing using the inventive adhesive may be appliedto the skin of a patient. When it is desired to remove or replace thedressing, the light occlusive layer part of the backing layer may beremoved. The adhesive on the skin-facing surface of the transparentlayer can then be exposed to either ambient light or an artificial lightsource, such as an incandescent lamp, a fluorescent lamp, LEDs, etc.After a given time the peel strength of the adhesive will be reduced,allowing the transparent layer to be removed from the patient's skin.

Thus, a dressing is provided as hereinbefore described comprising abacking layer and an adhesive layer, wherein the backing layer comprisesa removable light occlusive layer and a transparent layer intermediatethe occlusive layer and the adhesive layer and wherein the adhesivelayer comprises a switchable adhesive as hereinbefore described.

Any conventional known occlusive and transparent materials may be usedin the backing layer of the dressings of the invention. Preferreddressings are those which comprise a film backing layer, i.e., both theocclusive and transparent layers comprise a film, although other backinglayers such as fabric layers may be used.

The term “film” in this context means a thin sheet or web of material.Typically, it could be a thermoplastic polymer. In some circumstances, ametal foil could be used for the occlusive layer, for example where thetransportation or diffusion of moisture is of no importance.

Dressings of the invention may be manufactured using conventionalmethods, save for the use of the inventive switchable PSA in place of aconventional adhesive and the requirement not to expose the switchablePSA to light. The occlusive layer of the backing layer may be adhesivelybonded to the transparent layer or may be laminated thereto. The peelforce required to remove the occlusive layer from the transparent layermust be less than the peel strength of the switchable PSA in its tackyform, otherwise it will be difficult to selectively remove the occlusivelayer without perturbing the dressing before the switchable PSA isconverted to its non-tacky or low tack state.

Dressings of the invention are especially useful in the treatment ofwounds. Thus, according to a further feature of the invention, theinvention provides a method of treating a wound on a patient comprisingapplying a dressing as hereinbefore described to the wound of a patient.The method may also include the removal of the dressing by removing thelight occlusive layer of the dressing and then irradiating the adhesivethrough the transparent or translucent layer to render the adhesivenon-tacky.

Various medicinal agents may be incorporated into the adhesivecompositions of the present invention. By medicinal agent is meantpharmacologically active agents including agents which are topicalanaesthetics such as xylocaine, bacteriostatic agents such as silvernitrate; anti-bacterial agents of which preferred forms are silversulphadiazine and chlorhexidine salts; antibiotics; topical steroids,enzymes; tissue stimulants; coagulants and anticoagulants and antifungalagents. Other agents such as emollients may also be added. The effect ofsuch agents may contribute to the method of treatment using dressings ofthe invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be illustrated by way of example only withreference to the drawings, in which:

FIG. 1 is a cross-section of an adhesive tape using a switchableadhesive in accordance with the invention;

FIG. 2 is a cross-section of a dressing of the invention, and

FIG. 3 is a schematic cross-sectional view of a simple adhesive labelusing the switchable adhesive of the invention.

FIG. 4 is a graph showing the change in peel force with differentamounts of cross-linker for various switchable PSAs formulated inaccordance with Example 6.

FIG. 5 is a graph showing the change in dynamic shear force withdifferent amounts of cross-linker for various switchable PSAs formulatedin accordance with Example 6.

FIG. 6 is a graph showing the change in peel force with differentamounts of cross-linker for various switchable PSAs formulated inaccordance with Example 7.

FIG. 7 is a graph showing the change in dynamic shear force withdifferent amounts of cross-linker for various switchable PSAs formulatedin accordance with Example 7.

FIG. 8 is a graph showing the change in peel force with differentamounts of cross-linker for various switchable PSAs formulated inaccordance with Example 8.

FIG. 9 is a graph showing the change in dynamic shear force withdifferent amounts of cross-linker for various switchable PSAs formulatedin accordance with Example 8.

Referring to FIG. 1, an adhesive tape is designated by reference numeral1. The tape comprises a backing layer 2 and an adhesive layer 3. Thebacking layer 2 comprises an occlusive layer 4 and a transparent layer 5intermediate the occlusive layer 4 and the adhesive layer 3. The tapemay optionally be provided with appropriate carrier layers and protectorlayers.

Such an adhesive tape could be in the form of a surgical tape formedical applications. In use, the tape 1 is adhered to the skin of apatient when the adhesive layer 3 is in a tacky state. When it isdesired to remove the tape 1 from the patient's skin, the occlusivelayer 4 is removed to reveal the transparent layer 5 and thereby exposethe adhesive layer 3 to visible light. The visible light causes thephotoinitiator to initiate free-radical cross-linking of the pressuresensitive adhesive through the curable molecules incorporated in theadhesive mix. This results in the adhesive losing its tackiness and peelstrength. The time required for complete switching of the adhesive fromthe tacky state to the non-tacky state may vary, e.g., from a fewseconds to several minutes. The tape may then be removed from thepatient's skin with reduced trauma to the patient.

Referring now to FIG. 2, this shows a schematic cross-section of amedical dressing according to the present invention when in use on apatient.

Medical dressing 10 is shown attached to a patient's skin 20. Thedressing 10 comprises a wound facing absorbent layer 30 disposed beneatha protective backing layer 40. At opposed edges 50, 60, the backinglayer 40 is provided with adhesive 70 which comprises groups that can becross-linked under the influence of visible and/or UV light.

The backing layer 40 is provided with a cover 80 which is releasablysecured to the backing layer 40 by a weak adhesive 90. In an alternativearrangement, not shown here, the cover 80 may be laminated to thebacking layer 40. For ease of removal, the cover 80 overlaps the backinglayer 40 at its edges 100, 110.

When it is desired to remove the dressing from the skin of the patient,the cover 80 can be gripped at its edges 100, 110 and peeled from thebacking layer 40 to expose the adhesive 70 to UV or visible lightirradiation. This irradiation acts so as to generate free radicals thatcause the curable molecules to undergo a curing reaction which, after acertain time (depending upon the adhesive used), causes the adhesive 70to lose its tackiness to such an extent that the dressing can be removedwithout causing trauma to the patient.

In order that the removal of the cover 80 does not itself cause traumato the patient, the peel strength of the adhesive 90 adhering the cover80 to the backing layer 40 should be less than the peel strength of theadhesive 70 adhering the dressing 10 to the patient's skin.

Since the adhesive 70 loses tackiness on exposure to visible and/or UVlight, it is desirable that the adhesive 70 is not exposed to the lightfor a substantial period when the dressing 10 is applied to a patient.Thus, the adhesive 70 may be initially provided on the surface withrelease paper (not shown) which is preferably opaque to UV and visiblelight and which can be readily removed from the adhesive so that thedressing is ready for use when required.

It is another requirement of the constituents of the adhesive mixtureused in medical applications that they should be capable of undergoingsterilisation without causing switching of the adhesive from its tackystate to a non-tacky state. High-temperature sterilisation byautoclaving is not appropriate for medical products and/or utensils thatare sensitive to heat; ethylene oxide sterilisation can be used instead.

In many applications, a release film or release paper layer is appliedover the switchable PSA layer and is removed just before the switchablePSA is applied to its working site. The release layer needs to be lightocclusive to prevent switch of the switchable PSA during storage. Asexamples, the release layer may be a black siliconized PET film, or aPET film with an aluminium foil laminated to it.

Turning now to FIG. 3, this shows in a schematic cross-sectional viewhow the invention can be applied to a simple two-layer device such as aremovable product label.

The label is generally denoted by the reference 210 and comprises anadhesive layer 213 composed of switchable adhesive in accordance withthe present invention, and an occlusive layer 214 (which may be in theform of a film) overlying the adhesive layer and preventing access oflight to the adhesive layer. In this embodiment, the occlusive layer isalso provided with a peel tab 215 that facilitates removal of the labelfrom the product surface to which it is applied.

It is not essential in the case of a removable product label for thepeel force required to remove the occlusive layer to be less than thepeel force required to remove the adhesive in its tacky form from theproduct. In practice, it may be preferred if some of the adhesive layeris removed with the occlusive layer. The residue of the adhesive whichremains on the product is then able to switch to its non-tacky statethrough exposure to light. The non-tacky adhesive residue can be easilyremoved from the product surface by rubbing or washing.

The occlusive layer 214 may have a design/indicia on its surface. Insome embodiments, the design/indicia may provide the occlusive effectand may therefore be disposed at the interface between the occlusivelayer 214 and the adhesive layer 213 so that it is protected fromscuffing damage.

As mentioned above, one problem associated with switchable adhesiveshaving bound-in curable groups is that they require painstakingsynthesis. Also, they often require switching times of more than 1minute. In particular, the polymerisation of acrylate internallyfunctionalised switchable adhesives requires the use of multiplesolvents, firstly in order to produce a polymer having a sufficientlyhigh molecular weight and low monomer concentration for suitability as amedical adhesive, and secondly to carry out the reaction of thefunctionalising moiety with the main polymer chain.

An adhesive manufacturing process requiring multiple solvents, and hencesolvent exchange steps, is complicated, time consuming and expensive.

By contrast, the switchable adhesives of the present invention can bemade from a mixture of readily available adhesives and curable monomersor oligomers containing acrylate functions which, upon irradiation, formchemical bonds between the oligomers or monomers and hence createpolymeric cross-linking. The effect of such cross-linking is to build athree-dimensional polymeric network interlocking with the adhesivepolymer chains, thereby reducing their mobility and free volume. Thischange, which takes place very quickly, causes the PSA to become lowtack. The force required to peel the adhesive has been found to reduceconsiderably, by at least 60% to 90%, after illumination.

Examples of suitable curable monomers and oligomers, used alone or inmixtures, are acrylic acid esters or methacrylic acid esters ofalcohols, glycols, pentaerythritol, trimethylpropane, glycerol,bisphenol A epoxides, aliphatic epoxides, aromatic epoxides, aliphaticurethanes, aromatic urethanes, silicones, polyesters and polyethers aswell as ethoxylated or propoxylated species thereof.

The invention will now be further illustrated with reference toExamples. In the Examples below, the constituents are listed in theorder:

1 base adhesive(s)

2 curable molecules

3 photoinitiator and, where present,

4 stabilizer for preventing premature switch during storage

5 Stabilizer of internal cross-linker in solution.

6 Internal cross-linker.

EXAMPLE 1

Component Amount (g)  1a Aroset 1450 Z 40 100.60  1b Aroset 1450 Z 40*0.00 2 CN 925 33.10 3 Irgacure 784 0.52 4 Irganox 1010 0.10 *withoutinternal cross-linker

EXAMPLE 2

Component Amount (g)  1a Aroset 1450 Z 40 26.24  1b Aroset 1450 Z 40*15.82 2 CN 925 10.43 3 Irgacure 784 0.30 4 Irganox 1010 0.03 *withoutinternal cross-linker

EXAMPLE 3

Component Amount (g)  1a Aroset 1450 Z 40 23.14  1b Aroset 1450 Z 40*21.87 2 Omnilane P9200Z 14.61 3 Irgacure 784 0.32 4 Irganox 0.05*without internal cross-linker

COMPARATIVE EXAMPLE 4

Component Amount (g)  1a Aroset 1450 Z 40 20.00  1b Aroset 1450 Z 40*20.00 2 CN 925 12.10 3 Irgacure 784 0.22 4 Irganox 0.03 *withoutinternal cross-linker

COMPARATIVE EXAMPLE 5

Component Amount (g)  1a Aroset 1450 Z 40 0.00  1b Aroset 1450 Z 40*37.60 2 CN925 5.40 3 Irgacure 784 0.51 4 Irganox 0.03 *without internalcross-linker

EXAMPLE 6

To a master batch consisting of:

Component Amount (w/w %) 1 GMS 1753u 73.6 2 CN925 20.8 3 Irgacure 7840.41 4 Irganox 1010 0.05 5 Methanol 5.1a poly(melamine-co-formaldehyde), methylated solution (6) was added to afinal concentration of 0, 0.31, 0.48, 0.62 and 0.77 weight percent, intotal five samples, in preparation for peel and shear tests. The resultsare tabulated in Tables 3 and 4 and illustrated in FIGS. 4 and 5.

EXAMPLE 7

To a master batch consisting of:

Component Amount (w/w %) 1 Aroset 1910-TH-52 62.4 2 Ebecryl 870 22.8 3Irgacure 784 0.4 4 Irganox 1010 0.1 5 Isopropanol 14.2Aluminium acetylacetonate (6) was added to a final concentration of 0,0.035, 0.061, 0.11 0.21 and 0.77 weight percent, in total six samples,in preparation for peel and shear tests. The results are tabulated inTables 5 and 6 and illustrated in FIGS. 6 and 7.

EXAMPLE 8

To a master batch consisting of:

Component Amount (w/w %) 1 Polytex SP8002 75.2 2 CN925 23.5 3 Irgacure784 1.2 4 Irganox 1010 0.1 5 none 0Tolylene 2,4-diisocyanate (6) was added to a final concentration of 0,0.016, 0.025, 0.039, 0.054 and 0.097 weight percent, in total sixsamples, in preparation for peel and shear tests. The results aretabulated in Tables 7 and 8 and illustrated in FIGS. 8 and 9.

TABLE 1 Table of Suppliers Component Description Company Aroset 1450Thermosetting acrylic solution Ashland Inc. Z 40 polymer, dry content40% CN 925 Aliphatic urethane tetraacrylate Sartomer Co., Inc. (CrayValley SA) Omnilane Tri functional polyester acrylate IGM resins P9200ZB.V. Netherlands Irgacure 784 Bis.(.eta.5-cyclo-pentadienyl)-bis CibaSpecialty (2,6-difluoro-3-[pyrrol-l-yl]-phenyl) Chemicals titaniumIrganox 1010 Pentaerythritol Tetrakis(3-(3,5-di- Ciba Specialtytert-butyl-4-hydroxyphenyl) Chemicals propionate Hostaphane 23 myPolyester film Mitsubishi RNK 2600 Polyester Film SP 8002 Acrylicadhesive dry content 45% Avery Dennison Aroset Acrylic adhesive with0.1-0.5%, Ashland Inc 1910-TH-52 according to MSDS, aluminiumpentadionate as a cross-linker dry content 52% GMS 1753u Acrylicadhesive dry content 42% Poly(melamin-co- Cross-linker Sigma-Aldrichformaldehyde), methylated [or polyhexamethoxy methyl melamine] 84 wt. %solution in 1-butanol Aluminium Cross-linker Sigma-Aldrichacetylacetonate, ReagentPlus, 99% Tolylene 2,4- Cross-linkerSigma-Aldrich diisocyanate, 95% Ebecryl 870 Polyester acrylate CytecHostaphane 50 my Polyester film Mitsubishi RNK 2600 Polyester Film

Preparative Details

All components in the respective examples were loaded into a sealableglass jar and mixed to a homogenous solution over a period ofapproximately 60 minutes under red light conditions using a magneticstirrer. The resulting adhesive solution was then spread onto a releaseliner using a spreader to a coating thickness of about 60 μm and left todry at room temperature for 10 minutes.

The adhesive coating was then further dried in a ventilated fan assistedoven at 110° C. for an additional 10 minutes. After drying, thethickness of the adhesive coating was about 30 μm.

Finally, for peeling studies, a 23 μm Hostaphane RNK 2600 (polyester)film was transferred to the exposed side of the adhesive in preparationfor peeling studies. For the dynamic shear tests, a 50 μm RNK 2600(polyester) film was used; a thicker film was necessary in order toprevent film expansion during the tests. All procedures using Irgacure784 were carried out under red light conditions.

Peel Force Measurements

Peel strengths were determined after a dwell time of 20 minutes using aLLOYD testing rig (L2000R) according to FINAT test method FTM1, with theexception that high density polyethylene (HDPE) plates were used as thesubstrate and that a peeling rate of 100 mm/min was used in order tocollect all of the necessary data within the time frame of one peelforce measurement.

Dynamic Shear Strength Measurements

Dynamic shear strength was obtained according to Finat test method(Finat technical handbook 6^(th) edition 2001) FTM18 utilizing the sameinstrument as above.

Adhesive switching was achieved by exposing the adhesive film (adheredto the HDPE plate) to light through the PET carrier film backing with alight intensity of approximately 12000 lux from a 500 W halogen lamphaving a broad spectrum. It should be noted that switching timesachievable with a light source intended for consumers (LEDs with spectraadjusted to the photoinitiator) will be less than the values obtainedwith the broad spectrum lamp mentioned above. However, using a lightsource in these tests that is adjusted to the photoinitiator would makeit difficult to get an accurate measurement of the switching time forpurposes of comparison, since the switching times would all have beenvery short. Switching times for the different coatings were measured asthe time between the starting time of irradiation and the time when thesubstantially instantaneous loss of tack occurred, during a continuouspeel strength test of about 1 minute (i.e., the adhesive was peeled fora period of time whilst being irradiated). Peel strengths and switchingtimes were measured in quadruple and the average values of switch timeand peel strength (before and after switch) were calculated.

Adhesive Switching

Results quoted below in Table 2 as %-switch refer to the percentagereduction in peel strength after exposure to light, calculated asfollows:(1−P1/P2)*100=%-switchwhere P1 is the peel strength after exposure to light and P2 is theinitial peel strength.

On the following pages, tables of peel strength test results and dynamicshear strength test results are provided.

Table 2 is a table of results of peel strength tests for Examples 1 to 3and comparative examples 4 and 5.

Table 3 is a table of results of peel strength tests for variousswitchable PSAs formulated in accordance with Example 6 with differentproportions of cross-linker, the peel force being measured before andafter switch. The results are also illustrated in FIG. 4.

Table 4 is a table of results of dynamic shear force tests for theswitchable PSAs formulated in accordance with Example 6 with theirdifferent proportions of cross-linker. The results are also illustratedin FIG. 5.

Table 5 is a table of results of peel strength tests for variousswitchable PSAs formulated in accordance with Example 7 with differentproportions of cross-linker, the peel force being measured before andafter switch. The results are also illustrated in FIG. 6.

Table 6 is a table of results of dynamic shear force tests for theswitchable PSAs formulated in accordance with Example 7 with theirdifferent proportions of cross-linker. The results are also illustratedin FIG. 7.

Table 7 is a table of results of peel strength tests for variousswitchable PSAs formulated in accordance with Example 8 with differentproportions of cross-linker, the peel force being measured before andafter switch. The results are also illustrated in FIG. 8.

Table 8 is a table of results of dynamic shear force tests for theswitchable PSAs formulated in accordance with Example 8 with theirdifferent proportions of cross-linker. The results are also illustratedin FIG. 9.

Table 9 is a summary table of the average values obtained from the shearand peel tests for the PSAs of Examples 6 to 8 with their differentproportions of cross-linker.

TABLE 2 Results of Peel Strength Tests Peel force Shear value Peel forceSwitch Example before switch before switch after switch time Number(N/25 mm) (minutes) (N/25 mm) (Seconds) %-switch Failure mode 12.04 >2000 0.11 3.75 94.60 CP 2 3.36 275 0.17 2.50 94.93 CP 3 3.7 1250.45 5.70 87.84 CP 4 5.0 75 0.2 3.05 96.00 PCF 5 15.5 16 0.45 2.15 97.10CF Key to failure modes CP = Clean Panel, i.e., no residuals left on thetest plate PCF = Partial Cohesive Failure, i.e., some adhesive left onthe test plate CF = Cohesive Failure

TABLE 3 Results of peel force tests on Examples 6 Peel force (N/25 mm) Xlinker before switch Peel force (N/25 mm) after switch Switch time (s)%- Coat weight (wet w/w %) S1 S2 S3 S4 Average Failure mode S1 S2 S3 S4Average S1 S2 S3 S4 Average Switch (g/m²) 0.00 6.1 7.6 7.0 7.4 7.02 PCF0.11 0.11 0.11 0.12 0.11 3.0 3.0 3.0 3.0 3.0 98.4 39 0.14 5.9 5.3 3.63.4 4.52 CP 0.23 0.13 0.17 0.16 0.17 3.3 3.3 3.3 3.0 3.2 96.2 36 0.313.3 3.5 4.2 n/a 3.69 CP 0.18 0.15 0.12 0.37 0.15 3.0 3.0 3.0 3.0 3.095.9 37 0.47 2.8 2.9 3.3 2.9 2.97 CP 0.19 0.16 0.17 0.20 0.18 3.0 3.03.0 2.8 2.9 93.9 36 0.62 1.9 2.1 2.3 2.5 2.19 CP 0.12 0.15 0.13 0.100.13 3.3 3.0 3.0 3.0 3.1 94.3 34 0.77 1.3 1.3 1.8 1.7 1.54 CP 0.15 0.130.12 0.16 0.14 3.0 3.0 3.0 3.0 3.0 90.9 37

TABLE 5 Results of peel force tests on Examples 7 Peel force (N/25 mm) Xlinker before switch Peel force (N/25 mm) after switch Switch time (s)%- Coat weight (wet w/w %) S1 S2 S3 S4 Average Failure mode S1 S2 S3 S4Average S1 S2 S3 S4 Average Switch (g/m²) 0.00 7.3 6.1 7.5 6.7 6.97 CP0.15 0.10 0.18 0.21 0.16 4.2 4.0 3.9 4.0 4.0 97.7 29 0.035 6.8 6.0 6.55.9 6.43 CP 0.17 0.20 0.25 0.20 0.21 4.0 4.0 4.0 4.5 4.1 96.8 31 0.0616.5 7.1 5.9 5.0 6.50 CP 0.25 0.39 0.30 0.25 0.30 4.0 4.3 4.3 4.3 4.295.4 34 0.114 3.7 3.0 2.9 3.3 3.17 CP 0.21 0.20 0.19 0.18 0.20 4.5 4.03.8 4.0 4.1 93.8 31 0.212 1.9 2.1 2.3 2.3 2.11 CP 0.15 0.20 0.14 0.190.17 4.5 4.0 4.5 4.0 4.3 91.9 29 0.387 0.9 1.2 1.2 1.10 CP 0.21 0.170.16 0.18 5.5 5.0 4.8 5.1 83.6 33

TABLE 7 Results of peel force tests on Examples 8 Peel force (N/25 mm) Xlinker Peel force (N/25 mm) before switch after switch Switch time (s)Coat (wet Aver- Failure Aver- Aver- %- weight w/w %) S1 S2 S3 S4 agemode S1 S2 S3 S4 age S1 S2 S3 S4 age Switch (g/m²) 0.00 7.9 5.3 6.2 6.26.65 CF 0.60 0.95 0.33 0.43 0.58 15.2 14.0 10.5 12.4 13.0 91.3 34 0.01512.0 12.9 (4.4 11.5 12.13 CF 0.88 0.63 0.41 0.67 0.65 12.0 11.3 12.511.5 11.8 88.1 29 CP) (6.5 CP) 0.025 3.0 3.4 6.0 5.3 4.43 CP 0.50 0.460.65 0.39 0.50 13.0 14.0 13.0 12.5 13.1 88.7 35 0.039 2.9 4.1 3.7 3.53.55 CP 0.53 0.41 0.60 0.60 0.54 13.0 13.0 12.3 13.0 12.8 84.9 36 0.0541.6 1.7 1.3 1.4 1.51 CP 0.50 0.37 0.40 0.38 0.41 14.5 15.0 15.0 15.515.0 72.7 34 0.097 1.0 0.9 1.0 1.0 0.96 CP 0.50 0.39 0.36 0.39 0.41 15.815.0 15.0 15.0 15.2 57.4 35

TABLE 4 Results of dynamic shear force tests on Examples 6 Coat x-linkerdynamic shear force (N/161 mm²) weight (wet w/w %) S1 S2 S3 S4 Averagefailure (g/m²) 0.000 4.91 4.82 4.82 4.96 4.88 CF 39 0.137 21.2 22.1 21.721.5 21.6 CF 36 0.311 31.2 34.3 33.7 32.9 33.0 CF 37 0.474 53.5 56.355.4 57.6 55.7 PCF 36 0.623 61.1 63.5 64.7 60.3 62.4 PCF 34 0.770 60.558.9 60.4 60.0 60.0 PCF 37

TABLE 6 Results of dynamic shear force tests on Examples 7 Coat x-linkerdynamic shear force (N/161 mm²) weight (wet w/w %) S1 S2 S3 S4 Averagefailure (g/m²) 0.000 38.8 39.5 39.6 35.5 38.3 CF 29 0.035 47.8 45.1 47.844.7 46.4 CF 31 0.061 53.0 52.7 50.4 45.9 50.5 PCF 34 0.114 49.2 55.955.0 55.0 53.8 CP 31 0.212 45.6 44.6 43.5 44.9 44.6 CP 29 0.387 45.338.8 37.7 37.6 39.8 CP 33

TABLE 8 Results of dynamic shear force tests on Examples 8 Coat x-linkerdynamic shear force (N/161 mm²) weight (wet w/w %) S1 S2 S3 S4 Averagefailure (g/m²⁾ 0.000 7.2 2.2 2.2 2.1 2.2 CF 34 0.016 15.8 15.8 16.5 15.115.8 CF 29 0.025 18.9 19.3 19.8 18.5 19.2 CF 35 0.039 32.4 35.5 35.635.7 35.6 CP 36 0.054 30.0 22.5 29.5 31.1 27.7 CP 34 0.097 34.0 31.438.5 35.2 35.1 CP 35

TABLE 9 Summary table of average values obtained from sheer and peeltests for Examples 6 to 8 Dynamic Dynamic Peel force Peel force Exampleshear force shear failure before after switch Switch time Peel failurenumber x linker (%) (N/161 mm²) mode switch (N/25 mm) (N/25 mm)(seconds) %-switch mode 6 0.00 4.88 CF 7.0 0.11 3.0 98.4 PCF 0.14 21.6CF 4.5 0.17 3.2 96.2 CP 0.31 33.0 CF 3.7 0.15 3.0 95.9 CP 0.47 55.7 PCF3.0 0.18 2.9 93.9 CP 0.62 62.4 PCF 2.2 0.13 3.1 94.3 CP 0.77 60.0 PCF1.5 0.14 3.0 90.9 CP 7 0.00 38.3 CF 7.0 0.16 4.0 97.7 CP 0.04 46.4 CF6.4 0.21 4.1 96.8 CP 0.06 50.5 PCF 6.5 0.30 4.2 95.4 CP 0.11 53.8 CP 3.20.20 4.1 93.8 CP 0.21 44.6 CP 2.1 0.17 4.3 91.9 CP 0.39 39.8 CP 1.1 0.185.1 83.6 CP 8 0.000 2.16 CF 6.7 0.58 13.0 91.3 CF 0.016 15.8 CF 5.5 0.6511.8 88.1 PCF 0.025 19.1 CF 4.4 0.50 13.1 88.7 CP 0.039 34.8 CP 3.6 0.5412.8 84.9 CP 0.054 28.3 CP 1.5 0.41 15.0 72.7 CP 0.097 34.8 CP 1.0 0.4215.0 56.1 CP

EXAMPLE 6 Adhesives

Referring to FIG. 4, the peel force decreases with increasing amount ofcross linker, which is because cross linking makes the adhesive morestiff and less capable of flow and of wetting the surface to it has beenattached. At the same time the switched peel force values staypractically independent of the concentration of internal cross-linker.This is due to the inter-molecular cross linking that takes place duringthe switch totally overwhelming the contribution of the intra-molecularcross linking used for controlling the tack-shear balance.

In opposition to this, as seen in FIG. 5, the dynamic shear forceincreases with increasing concentrations of internal cross linker up toa certain point, after which it declines. The increase at the beginningis explained by the cohesive strength being improved through crosslinking of the polymer chains. As a result, it requires an increasingamount of force to shear the adhesive. However this increase in shearforce reaches a maximum. Where the weakest point in the adherent chainceases to be the cohesive strength and instead changes to become theadhesive strength, the failure mode changes from cohesive failure (CF)to so-called “clean panel” (CP) where no residual adhesive is left onthe test plate. The decline after this point occurs because higher crosslinking makes the adhesive less capable of flow and less able to wet thetest surface, which thereby lowers the adhesive force. It is possiblethat some of the decrease observed here can can be attributed tostretching the film above the adhesive. A tendency to stretching of thefilm also was the reason for using a thicker film during the dynamicshear tests compared to the film used for the peel tests. The reasoningfor not including the switched values in the dynamic shear force graphis that, at least for low concentration of cross linker, in this casethe PSA will benefit from good wetting and flow properties when firstapplied to the surface and from a very high shear strength afterswitching it, which often will result in breaking the carrier film. Thisis a phenomenon that can find a number of applications where the productis not exposed to any significant peel force but where high shearstrength and/or residual-free removal is of great importance.

EXAMPLE 7 Adhesives

Referring to FIGS. 6 and 7, the graphs for peel force and shear force,respectively, for Example 7 basically follow the same pattern as inExample 6 with the exception that the maximum value in shear forceappears in the middle of the explored concentration range of crosslinker.

EXAMPLE 8 Adhesives

Referring now to FIGS. 8 and 9, the graphs for peel and shear force forthe various Example 8 adhesives, mimic the earlier described examplesexcept for a maximum in peel force in the unswitched state presentsomewhere around 0.016% concentration of cross linker. In fact, thebalance between CF and CP is so delicate at this concentration, as canbe seen from the line of peel force values in Table 7 at 0.016 wet w/w %cross-linker, that while some samples show CF others show CP or evenchanges between CF and CP during the peel. The reason for the maximum inthe peel force curve mirrors the one present in the dynamic shear forcevalues mentioned earlier. When the failure changes from CF to CP theforce needed to detach the adhesive from the test surface decreases.That the decline is more abrupt here than in the shear force curves ismost probably due to the energy loss from forcing the adhesive to flowand split during a peel test under CF is much higher than during a sheartest because they take place at different rates, namely 100 and 5mm/min, respectively. Also, the peel force value is an average numberwhile the shear force value is the maximal value of the shear forcecurve.

Note that, in some applications, a partial cohesive failure leaving onlya small residue of adhesive behind after switching will be acceptable.

An adhesive composition which might find application in a medicaldressing for use in treating a chronic wound or a permanent stoma thatneeds dressing repeatedly and where, if a non-switchable adhesive wereused, skin trauma would be significant is an adhesive that exhibitsstrong adhesion in the unswitched state. After switching, the adhesiveshould have a significantly reduced peel force. A medical dressing usingthis adhesive could be easily removed after switching without causingdiscomfort to the patient or traumatising fragile skin.

An adhesive suitable for very sensitive materials e.g. delicateproduction line work is one which has an initial tackiness that issufficient to position components reliably on a production line forcertain steps in a production process. An occlusive layer may be removedat this low tackiness without perturbing the components. Afterswitching, the peel force should be reduced to an almost negligiblevalue, allowing the processed components to be removed easily from theproduction line.

The present invention is not limited to use in adhesive dressings.Examples of other technical applications include: removable labels; forshipping and handling of fragile or sensitive parts; production lineapplications where one or several pieces attached to a switchable PSAtape can be mounted into a structure—the tape can then easily be removedafter irradiation. Other examples are vehicle labels, shop floormarkers, wallpaper and adhesive fixings for posters and/or notices.

The invention claimed is:
 1. A switchable pressure sensitive medicaladhesive composition comprising a mixture, in proportions by weightbased on the weight of the composition, of: 20% to 98% of a baseadhesive polymer constituent which has no bound-in curable groups thatare curable by free radical polymerization; 2% to 80% of curablemolecules that are curable by free radical polymerization and have aminimum weight average molecular weight of 500 dalton, and 0.05% to 10%of a photoinitiator, wherein the weight proportion of the base adhesiveis calculated on the basis of its dry weight and wherein saidcomposition includes an internal cross-linker that is curable by amechanism other than free radical polymerization for cross-linking theadhesive during drying to provide a cohesive strength of between 5 and100 N/12.7×12.7 mm measured according to FINAT test method No.
 18. 2. Aswitchable pressure sensitive medical adhesive composition according toclaim 1 comprising a mixture, in proportions by weight based on theweight of the composition, of: 40% to 98% of the base adhesive polymerconstituent; 2% to 60% of the curable molecules, and 0.5% to 5% of thephotoinitiator.
 3. A switchable pressure sensitive medical adhesivecomposition according to claim 1 comprising a mixture, in proportions byweight based on the weight of the composition, of: 60% to 95% of thebase adhesive polymer constituent; 5% to 40% of the curable molecules,and 0.5% to 5% of the photoinitiator.
 4. A switchable pressure sensitivemedical adhesive composition according to claim 1 comprising a mixture,in proportions by weight based on the weight of the composition, of: 70%to 85% of the adhesive polymer constituent; 15% to 30% of the curablemolecules, and 1% to 3% of the photoinitiator.
 5. A switchable pressuresensitive medical adhesive composition according to claim 1 wherein theproportion of internal cross-linker is from 0.1 to 6% in proportion byweight based on the wet base adhesive polymer constituent.
 6. Aswitchable pressure sensitive medical adhesive composition as claimed inclaim 1 wherein the base adhesive polymer constituent is selected fromthe group consisting of polyacrylates, polyurethanes and polysilicones.7. A switchable pressure sensitive medical adhesive composition asclaimed in claim 1 wherein the base adhesive polymer constituent is amixture of at least two adhesives selected from a group consisting ofpolyacrylates, polyurethanes and polysilicones.
 8. A switchable pressuresensitive medical adhesive composition as claimed in claim 1 wherein thebase adhesive polymer constituent is a polyacrylate.
 9. A switchablepressure sensitive medical adhesive composition according to claim 1wherein the curable molecules are unsaturated compounds.
 10. Aswitchable pressure sensitive medical adhesive composition according toclaim 9 wherein the curable molecules have more than one unsaturatedsite.
 11. A switchable pressure sensitive medical adhesive compositionaccording to claim 10 wherein the curable molecules have multiplefunctionalities of 3 or greater.
 12. A switchable pressure sensitivemedical adhesive composition as claimed in claim 1 wherein the curablemolecules are selected from the group consisting of acrylic acid estersand methacrylic acid esters of alcohols, glycols, pentaerythritol,trimethylpropane, glycerol, aliphatic epoxides, aromatic epoxides,aliphatic urethanes, silicones, polyesters, polyethers, ethoxylatedspecies thereof, propoxylated species thereof, or mixtures thereof. 13.A switchable pressure sensitive medical adhesive composition as claimedin claim 1 wherein the photoinitiator is selected from the groupconsisting of titanocene photoinitiators; dye/co-initiator systems;dye/borate salt systems; dye/peroxide systems and1,2-diketone/co-initiator systems.
 14. A switchable pressure sensitivemedical adhesive composition as claimed in claim 1 wherein thephotoinitiator is reactive to visible light.
 15. A switchable pressuresensitive medical adhesive composition as claimed in claim 1 wherein thereduction in peel force of the pressure sensitive adhesive afterswitching is 30 to 98%.
 16. A switchable pressure sensitive medicaladhesive composition as claimed in claim 15 wherein the reduction inpeel force of the pressure sensitive adhesive after switching is 50 to95%.
 17. A method for manufacturing a switchable pressure sensitivemedical adhesive composition according to claim 1, the method comprisingstirring the adhesive polymer constituent, the curable molecules, thephotoinitiator and the internal cross-linker together in darkness orunder red light conditions for 30 to 60 minutes at a temperature from10° C. to 40° C.
 18. A method for manufacturing a switchable pressuresensitive medical adhesive composition according to claim 17 wherein thestirring temperature is room temperature.
 19. A method for manufacturinga switchable pressure sensitive medical adhesive composition as claimedin claim 17 including a step of drying at 80° C. to 150° C.
 20. A methodfor manufacturing a switchable pressure sensitive medical adhesivecomposition as claimed in claim 17 further comprising spreading thecomposition onto a release means and drying the composition.